Pseudokryptogenin and its diacetate



1y, pseudo-kryptogenin.

Patented Oct. 8, 1946 7 UNITED" STATES PATENT} OFFICEy rsnvnokn rroennm AND ITS DIACETATE Romeo B. Wagner, State College, Pa., assig nor to Parke, Davis & Company, Detroit, Mich., a cor-'- poration of Michigan No Drawing. Application May 15, 1944, Serial No. 535,756

4 Claims. (Cl. 260-2395) This invention relates to the preparation of in a sealed tube for 10 hours. The solvent is new pseudo-sapogenins from certain steroidal removed in vacuo and the residue hydrolyzed with sapogenins which are described in J. Am. Chem. excess potassium bicarbonate (or alcoholic Soc. 65, 1199 (1943). These compounds are potash) in aqueous ethanol. The product is ether valuable as intermediates for the preparation of ext acted, crystallized from acetone and then rehormones of the sex hormone type and particucrystallized from ether to give pseudokryptogenin, larly of the adrenal cortex hormone type since M. P. 189192 C. A mixture of this product with they are oxygenated at position 12 of the steroid kryptogenin melts at 162167 C,

nucleus. AnaL: Calcd. for C27H40O3: C, 78.6; H, 9.8%.

The reaction by which steroidal sapogenins are Found: C, 78.5; H, 9.8%. isomerized to the pseudo-genins have been de- Treatment of pseudo-kryptogenin with hot scribed in detail in the copending Patents Nos. ethanolic hydrochloric acid converts it back into 2,352,848 and 2,352,852, issued July 4, 1944. These kryptogenin. The pseudo-kryptogenin of this also include proof of structure of the pseudoexamplehas the formula,

genin side chain. 15

This invention relates to the preparation of OH pseudo-genin compounds having the formula, H-

on HzOH 3 on. on, g 0 CH dB 3 Q- l pl H-OH: H V HY I I a I I; Pseudo-kryptogenin I Pseudolcryptogenin (from pennogem'n) A mixture of 6 grams of pennogenin acetate in where Y and are-918mm e glass 18 cc. of acetic anhydride is heated at 200 0. for

0H 10 hours. The mixture is evaporated in vacuo 1 on the steam bath and then re-evaporated with ethanol to remove the remaining acetic anhydride. After decolorizing a methanol solution of i gm? hydrolyzable to the residue with charcoal (Norite brand), the

0H product is crystallized from methanol and has 5 M. P. 68-73 C. It is further purified by hy- H drolysis with 5% ethanolic potash and crystallization from ether and then methanol to give a I have found that three sapogenins, Pennoenin, n'olog'enin and kryptogenin (see J. Am. giggggg gg fi' ibgfigg gi P' Wlth pseudo.

Chem. Soc., 65 1199-,--1943), when treated under the conditions described in Patents Nos. 2,352,848 g f' gg g g g and 2352 852 for isomerizing to pseudo-genins, I I

The diacetate is. prepared by refluxing pseudo.- are converted into the same pseudo-genm, namekrypbogenin with acetic 1 ydride, and crystaL lized from methanol to give material of M; ,P.

inventifn' may be illustrated by the 120-125 '0. Recrystallization from methanol 1Wmg exam! gives material of M. P. 115-125 and 124-126 c. pseudokr togenin om hr to enin) AnaL: Calcd for C31H4405-CH3OH: C, w f w 9 H, 9.2%. Found: 0, 72.5; H, 8.6%. Asolution of 5 grams of kryptogenin diacetate In a second run, the product from 20 g. of

m 15 cc. of acetic anhydride is heated at 200 C. pennogenin acetate and 25 cc. of acetic anhydride is hydrolyzed directly and then crystallized from acetone to give 11 g. of pseudokryptogenin.

The transformations of this example may be illustrated as follows:

oH-oH.

Pennogenin acetate A020 lat 200 0.

on on Hydrolysis Pscudo-kryptogenin,diacetate.

CHsCHg v H-CH| HPO A AcO (alcoholic KOH) l omen all ho Pseudorkryptogenin Pseudokryptogenm (from noloyem'n) bnl lkcoi/ \J Nologenin diacetats The same products, pseudokryptogenin diacetate are obtained.

While for'ease of manipulation and economy the preferred isomerizing agent is acetic anhydride, other lower aliphatic acid anhydrides may also be used. The preferred temperature range lies between 190 and 200 C. although 'thefreaction also takes place as low as 170 or as high as 230". The example is intended as illustrative and the invention is not necessarily limited to the conditions and reactants therein cited.

In addition to using ethanolic KOH solution for hydrolyzing the acylated pseudogenin to the free genin, one can use any other suitable alkaline solution, for example one containing and its NaOH, K2003, KHCO3, NazcOs, NaHCOa or the like. If an alcohol is required to aid hydrolysis, this can be methanol or other lower aliphatic alcohol instead of ethanol.

What I claim is:

1. Compounds having the formula,

CH; CH: CH1 I C=C--CHz-CH1 CHY where Y and Y are members of the class consisting of and groups hydrolyzable to 2. Compounds having the formula.

CH: t c on on r: r 3 m-on,

oaY N where Y and Y are members of the class consisting of and organic carboxylic acid ester groups hydrolyzable to 3. Pseudokryptogenin having the formula, CH: CH: EH /CH,CHI

A =0 H-om HIOH 4. Pseudokryptogenin diacetate having the formula,

ROMEO B. WAGNER. 

